Selective CO2 hydrogenation to formic acid with multifunctional ionic liquids

The development of simple, cost-effective and sustainable methods to transform CO2 into feedstock chemicals is essential to reduce the dependence on fossil fuels of the chemical industry. Here, we report the selective and efficient catalytic hydrogenation of CO2 to formic acid (FA) using a synergist...

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Main Authors: Weilhard, Andreas, Qadir, Muhammad Irfan, Sans, Victor, Dupont, Jairton
Format: Article
Published: American Chemical Society 2018
Subjects:
Online Access:https://eprints.nottingham.ac.uk/49324/
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author Weilhard, Andreas
Qadir, Muhammad Irfan
Sans, Victor
Dupont, Jairton
author_facet Weilhard, Andreas
Qadir, Muhammad Irfan
Sans, Victor
Dupont, Jairton
author_sort Weilhard, Andreas
building Nottingham Research Data Repository
collection Online Access
description The development of simple, cost-effective and sustainable methods to transform CO2 into feedstock chemicals is essential to reduce the dependence on fossil fuels of the chemical industry. Here, we report the selective and efficient catalytic hydrogenation of CO2 to formic acid (FA) using a synergistic combination of an ionic liquid (IL) with basic anions and relatively simple catalysts derived from the precursor Ru3(CO)12]. Very high values of TON (17000) and TOF have been observed and FA solutions with concentrations of up to 1.2 M have been produced. In this system, the imidazolium based IL associated with the acetate anion acts as precursor for the formation of the catalytically active Ru-H species, catalyst stabilizer and as an acid buffer, shifting the equilibrium towards free formic acid. Moreover, the IL acts as an entropic driver (via augmentation of the number of microstates), lowering the entropic contribution imposed by the IL surrounding the catalytically active sites. The favorable thermodynamic conditions enable the reaction to proceed efficiently at low pressure pressures, and furthermore the immobilization of the IL onto a solid support facilitates the separation of FA at the end of the reaction.
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spelling nottingham-493242020-05-04T19:26:26Z https://eprints.nottingham.ac.uk/49324/ Selective CO2 hydrogenation to formic acid with multifunctional ionic liquids Weilhard, Andreas Qadir, Muhammad Irfan Sans, Victor Dupont, Jairton The development of simple, cost-effective and sustainable methods to transform CO2 into feedstock chemicals is essential to reduce the dependence on fossil fuels of the chemical industry. Here, we report the selective and efficient catalytic hydrogenation of CO2 to formic acid (FA) using a synergistic combination of an ionic liquid (IL) with basic anions and relatively simple catalysts derived from the precursor Ru3(CO)12]. Very high values of TON (17000) and TOF have been observed and FA solutions with concentrations of up to 1.2 M have been produced. In this system, the imidazolium based IL associated with the acetate anion acts as precursor for the formation of the catalytically active Ru-H species, catalyst stabilizer and as an acid buffer, shifting the equilibrium towards free formic acid. Moreover, the IL acts as an entropic driver (via augmentation of the number of microstates), lowering the entropic contribution imposed by the IL surrounding the catalytically active sites. The favorable thermodynamic conditions enable the reaction to proceed efficiently at low pressure pressures, and furthermore the immobilization of the IL onto a solid support facilitates the separation of FA at the end of the reaction. American Chemical Society 2018-01-11 Article PeerReviewed Weilhard, Andreas, Qadir, Muhammad Irfan, Sans, Victor and Dupont, Jairton (2018) Selective CO2 hydrogenation to formic acid with multifunctional ionic liquids. ACS Catalysis, 8 . pp. 1628-1634. ISSN 2155-5435 Carbon dioxide; Hydrogenation; Ionic liquids; Formic acid; Selective; Mild; Sustainable http://pubs.acs.org/doi/10.1021/acscatal.7b03931 doi:10.1021/acscatal.7b03931 doi:10.1021/acscatal.7b03931
spellingShingle Carbon dioxide; Hydrogenation; Ionic liquids; Formic acid; Selective; Mild; Sustainable
Weilhard, Andreas
Qadir, Muhammad Irfan
Sans, Victor
Dupont, Jairton
Selective CO2 hydrogenation to formic acid with multifunctional ionic liquids
title Selective CO2 hydrogenation to formic acid with multifunctional ionic liquids
title_full Selective CO2 hydrogenation to formic acid with multifunctional ionic liquids
title_fullStr Selective CO2 hydrogenation to formic acid with multifunctional ionic liquids
title_full_unstemmed Selective CO2 hydrogenation to formic acid with multifunctional ionic liquids
title_short Selective CO2 hydrogenation to formic acid with multifunctional ionic liquids
title_sort selective co2 hydrogenation to formic acid with multifunctional ionic liquids
topic Carbon dioxide; Hydrogenation; Ionic liquids; Formic acid; Selective; Mild; Sustainable
url https://eprints.nottingham.ac.uk/49324/
https://eprints.nottingham.ac.uk/49324/
https://eprints.nottingham.ac.uk/49324/